EP2644668B1 - Uv curable coating composition having self-healing capabilities, coating film and method for preparing coating film - Google Patents

Uv curable coating composition having self-healing capabilities, coating film and method for preparing coating film Download PDF

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Publication number
EP2644668B1
EP2644668B1 EP12746954.2A EP12746954A EP2644668B1 EP 2644668 B1 EP2644668 B1 EP 2644668B1 EP 12746954 A EP12746954 A EP 12746954A EP 2644668 B1 EP2644668 B1 EP 2644668B1
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EP
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Prior art keywords
meth
acrylate
compound
accordance
polylactone
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EP12746954.2A
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German (de)
English (en)
French (fr)
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EP2644668A2 (en
EP2644668A4 (en
Inventor
Hye-Min Kim
Yeong-Rae Chang
Heon Kim
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LG Chem Ltd
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LG Chem Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/023—Silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the present invention is directed to UV-curable coating compositions with self-healing capabilities, coating films, and methods of producing coating films. More specifically, the present invention is directed to a UV-curable coating composition having high transmittance and a low level of haze, excellent scratch resistance and self-healing capabilities, a coating film prepared from the coating composition, and a method of producing the coating film.
  • Different coating layers or coating films are applied to the surfaces of electronic devices such as mobile phones, electronic material parts, home appliances, exterior or interior parts for vehicles, and plastic molded products, for the purpose of protecting the products from damage caused by mechanical, physical, or chemical influences from the outside.
  • electronic devices such as mobile phones, electronic material parts, home appliances, exterior or interior parts for vehicles, and plastic molded products
  • coating layers or coating films are applied to the surfaces of electronic devices such as mobile phones, electronic material parts, home appliances, exterior or interior parts for vehicles, and plastic molded products, for the purpose of protecting the products from damage caused by mechanical, physical, or chemical influences from the outside.
  • scratches occurring on the surface of the product coatings or cracks resulting from external impacts may lead to deterioration of external appearance and main performance of the products and shorten their lifespan, considerable researches have been conducted to protect the surface of the product and thus maintain long-term quality thereof.
  • Coating layers made from such compositions demonstrates self-healing capabilities to some extent for the cracks caused by an external impact, but they still have drawbacks such as unsatisfactory mechanical properties including scratch resistance or durability and poor compatibility between the components.
  • EP 2 261 289 A1 discloses a composition for coating a plastic substrate, said composition comprising silica particles having (meth)acryloyl groups; a hexafunctional or higher aliphatic urethane (meth)acrylate; and an active energy beam-curable compound having an alicyclic structure; wherein an amount of the silica particles is within a range from 1.0 to 40 mass%.
  • EP 1 544 857 A1 discloses a coating composition containing (A) a reactive particle wherein an organic compound having at least one polymerizable unsaturated group in its molecule is chemically bonded to an inorganic oxide particle; (B) a monomer or oligomer of an organic compound having at least two polymerizable unsaturated groups in its molecule; and (C) an organic compound with a weight average molecular weight of at least 1500 and having at least one polymerizable unsaturated group in its molecule.
  • WO 2008/039228 A1 discloses an UV-curable coating composition comprising acrylated silica particles, a solvent, a resin binder having acrylate groups, solvent and a photoinitiator.
  • WO 2009/069974 A2 discloses a coating composition comprising a solvent, an urethane acrylate, a photoinititaior and silica particles having acrylate groups chemically bound to their surface.
  • the present invention s provides a UV-curable coating composition having high transmittance, a low level of haze, and excellent scratch resistance and self-healing capabilities.
  • the present invention provides a coating film prepared by using the coating composition.
  • the present invention provides a method of producing the coating film.
  • the present invention provides a coating composition
  • a coating composition comprising a (meth)acrylate binder resin, a UV initiator, an organic solvent, and silica particles having a polylactone-modified hydroxyalkyl (meth)acrylate linked to their surface through a urethane linkage.
  • the present invention provides a coating film including a cured product of the coating composition.
  • the present invention provides a method of producing a coating film, which includes the steps of mixing a (meth)acrylate binder resin, a UV initiator, an organic solvent, and silica particles having a polylactone-modified hydroxyalkyl (meth)acrylate linked to their surface through a urethane linkage, applying the mixture to a substrate and drying it, and subjecting the dried mixture to UV curing.
  • UV-curable coating compositions More detailed explanations as to the UV-curable coating compositions, the coating films, and the production method of the coating films according to specific embodiments of the present inventions will be presented hereinbelow.
  • (meth)acrylate is intended to include both methacrylate and acrylate.
  • a coating composition including a (meth)acrylate binder resin, a UV initiator, an organic solvent, and silica particles having a polylactone-modified hydroxyalkyl (meth)acrylate linked to their surface through a urethane linkage is provided.
  • a coating composition obtained by adding silica particles having a polylactone-modified hydroxyalkyl (meth)acrylate linked to their surface through a urethane linkage to a (meth)acrylate binder resin can be used to produce a coating material with high transmittance and a low level of haze, an excellent level of scratch resistance, and self-healing capabilities.
  • the coating composition employs a highly flexible (meth)acrylate binder resin to extend spaces existing in the polymer network of the crosslinked structure and increase elasticity, thereby imparting enhanced self-healing capabilities to the coating materials thus obtained.
  • a highly flexible (meth)acrylate binder resin to extend spaces existing in the polymer network of the crosslinked structure and increase elasticity, thereby imparting enhanced self-healing capabilities to the coating materials thus obtained.
  • including the silica particles surface-treated with the (meth)acrylate compound in the coating composition results in a more compact crosslinked structure of the coating material thus obtained, thereby making it possible to enhance wear resistance and film strength and to prevent the coating material from being permanently damaged by large external forces or impacts and thus losing its self healing capabilities.
  • the silica particles having a polylactone-modified hydroxyalkyl (meth)acrylate linked to their surface through a urethane linkage are highly compatible with the (meth)acrylate binder resin, and may form chemical bonds through a UV curing process and play a role of a crosslinking point for the components in the coating material to increase scratch resistance and self-healing capabilities thereof.
  • the (meth)acrylate compound bonded to the surface of the silica particles may undergo a reaction with the (meth)acrylate binder resin under UV irradiation, acting to chemically link the silica particles and the binder resins.
  • the silica particles themselves have poor compatibility with a (meth)acrylate binder resin, they would be either segregated when being mixed in the coating composition (or the coating material) or partly aggregated in the coating composition (or the coating material).
  • the silica particles having a polylactone-modified hydroxyalkyl (meth)acrylate linked to their surface through a urethane linkage become highly compatible with the (meth)acrylate binder resin so that they can be uniformly mixed with the other components in the composition or the coating film.
  • the (meth)acrylate compound is bonded to the surface of the silica particles via a urethane linkage.
  • the silica particles have a (meth)acrylate compound bonded on its surface through a urethane linkage.
  • the chemical properties of the urethane linkage may bring about an increase in elasticity of the coating material thus obtained and more extended spaces present in the polymer network of the crosslinked structure in a final coating film or coating body to realize more enhanced self-healing capabilities.
  • the (meth)acrylate compounds being bonded to the surface of the silica particles via the urethane linkage make the silica particles have enhanced compatibility, allowing them to be uniformly mixed with other components in the composition or the coating film.
  • the (meth)acrylate compounds to be bonded to the surface of the silica particles includes a hydroxyalkyl (meth)acrylate modified with a polylactone compound.
  • the silica particles include silica particles surface-treated with a polylactone-modified hydroxyalkyl (meth)acrylate, and more preferably, silica particles having a polycaprolactone-modified hydroxyalkyl (meth)acrylate linked to its surface via a urethane linkage.
  • the polylactone compound may be a compound derived from a C3 to C10 cyclic ester, and preferably, a compound derived from a C4 to C8 cyclic ester, and more preferably a C6 cyclic ester. Accordingly, the polylactone-modified hydroxyalkyl (meth)acrylate compound may be a hydroxyalkyl (meth)acrylate compound having a polylactone compound linked to its end.
  • the silica particles having a polylactone-modified hydroxyalkyl (meth)acrylate linked to its surface via a urethane linkage may include a compound represented by Chemical Formula 2.
  • R 3 is hydrogen or methyl
  • R 4 is any divalent organic functional group
  • p is an integer of 1 to 5
  • q is an integer of 1 to 10
  • a is an integer equal to or greater than 1
  • b is an integer of 2 to 9
  • "silica" represents a silica particle.
  • R 4 may be a divalent organic functional group derived from a diisocyanate compound. Specific examples of the diisocyanate compound are the same as will be described below.
  • "a” may represent the number of the hydroxyalkyl (meth)acrylates modified with the polylactone compound that are linked to the surface of the silica particle via a urethane linkage, and for example, is an integer of 1 to 30.
  • b can be an integer of 3 to 7, and more preferably 5.
  • the silica particles may have an average diameter of 5 to 100 nm. Silica particles having an overly small size on average may fail to play a proper role of a crosslinking point or a support in the coating material, while those one having an overly large size on average may cause a decrease in transparency or mechanical properties of the coating material.
  • the (meth)acrylate binder resin refers to a polymer compound resin including an acrylate or methacrylate functional group, the types of which are not particularly limited.
  • Specific examples of the (meth)acrylate binder resin include a urethane (meth)acrylate resin and a hydroxyalkyl (meth)acrylate modified with a polylactone compound, a mixture thereof, or a copolymer therebetween.
  • the hydroxyalkyl (meth)acrylate resin modified with a polylactone compound may include a compound of Chemical Formula 1 as follows.
  • R 3 can be hydrogen or methyl
  • b can be an integer of 2 to 9
  • p can be an integer of 1 to 5
  • q can be an integer of 1 to 10.
  • b is an integer of 3 to 7, and more preferably, 5.
  • Specific examples of the hydroxyalkyl (meth)acrylate resin modified with the polylactone compound include Placcel FA (acrylate) series or Placcel FM (methacrylate) series, both of which are among the product lines from Daicel Co. Ltd.
  • the urethane (meth)acrylate resin refers to a polymer resin including an acrylate or methacrylate functional group and a urethane linkage (CO-NH) in its molecule, and specifically, it can be a polymer resin obtained from a reaction between a (meth)acrylate compound and an organic isocyanate compound having at least two isocyanate groups per molecule.
  • Preferred examples of the urethane (meth)acrylate resin include a reaction product between an organic isocyanate compound having at least two isocyanate groups per molecule and a hydroxyalkyl (meth)acrylate resin modified with a polylactone compound.
  • specific examples of the hydroxyalkyl (meth)acrylate resin modified with the polylactone compound may include a compound of Chemical Formula 1.
  • Specific examples of the organic isocyanate compound having at least two isocyanate groups per molecule are not particularly limited, and for example, may include any of diisocyanate compounds and polyisocyanate compounds having at least three isocyanate groups obtained by modification of the diisocyanate compound.
  • Examples of the modification method for the diisocyanate compound include an isocyanurate modification, a trimethylol propane modification, a biuret modification, and the like.
  • urethane (meth)acrylate resin examples include a compound of Chemical Formula 5 as follows.
  • R 3 is hydrogen or a methyl
  • p is an integer of 1 to 5
  • b is an integer of 2 to 9
  • q is an integer of 1 to 10.
  • r representing the number of the isocyanate groups in the organic isocyanate compound as used, may be, for example, an integer of 2 to 10, and preferably 2 to 6.
  • R 5 is an r-valent functional group derived from the organic isocyanate compound.
  • b can be an integer of 3 to 7, and more preferably 5.
  • the coating composition includes an organic solvent.
  • Any organic solvent known in the art to be available for the coating composition may be employed without any particular limitation.
  • a ketone organic solvent such as methyl isobutyl ketone, methyl ethyl ketone, dimethyl ketone, and the like
  • an alcohol organic solvent such as isopropyl alcohol, isobutyl alcohol, and normal butyl alcohol
  • an acetate organic solvent such as ethyl acetate, normal butyl acetate, and the like
  • a cellosolve organic solvent such as ethyl cellosolve, butyl cellusolve, and the like.
  • the organic solvent is not limited to the aforementioned ones.
  • the coating composition includes a UV initiator.
  • a UV initiator Any known UV initiator typically available in the art may be utilized with no particular limitations. For example, one may use a benzophenone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an oxime compound, or a mixture thereof.
  • UV initiator examples include benzophenone, benzoyl methyl benzoate, acetophenone, 2,4-diethtyl thioxanthone, 2-chloro thioxanthone, ethyl anthraquinone, 1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure 184 marketed by Ciba Co., Ltd., and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.
  • the coating composition may include 20 % to 80 % by weight of a (meth)acrylate binder resin; 1 % to 10 % by weight of a UV initiator; 5 % to 50 % by weight of an organic solvent; and 1 % to 30 % by weight of a silica particle.
  • the coating composition may further include a UV-curable monomer.
  • the UV-curable monomer may act as an inter-polymeric crosslinker under UV irradiation, enhance workability of the coating composition, or take a part in making an improvement in the properties of the material obtained from the coating composition.
  • the coating composition may further include 1 % to 30 % by weight of the UV-curable monomer.
  • the UV-curable monomer may include a multifunctional acrylate compound having at least two functional groups.
  • Specific examples of such UV-curable monomer include, but are not limited to, pentaerythritol tri/tetraacrylate (PETA), dipentaerythritol hexa-acrylate (DPHA), trimethylol propane triacrylate (TMPTA), and hexamethylene diacrylate (HDDA).
  • the coating composition may further include an additive such as a leveling agent or a dispersion stabilizer in an amount of 0.1 % to 5 % by weight.
  • an additive such as a leveling agent or a dispersion stabilizer in an amount of 0.1 % to 5 % by weight.
  • a coating film including a cured product of the coating composition is provided.
  • silica particle when added to a certain (meth)acrylate binder resin and then subjected to UV curing, it is possible to produce a coating material that has high transmittance, a low level of haze, excellent scratch resistance, and superior self-healing capabilities.
  • the acrylate compound being linked to the surface of the silica particles would form a chemical bond with the (meth)acrylate binder resin, and thereby the silica particles are made to play a role of a crosslinking point between the components in the coating film, improving the coating material in terms of not only mechanical properties such as scratch resistance but also self-healing capabilities.
  • the coating film may include a (meth)acrylate binder resin, and silica particles to which the binder resin is chemically bonded.
  • a carbon-carbon double bond in the acrylate moiety of Chemical Formula 2 undergoes a reaction with a carbon-carbon double bond in the binder resin and thereby the silica particles may be chemically bonded to the binder resin.
  • the acrylate binder resin and silica particles may form a crosslinked network structure.
  • binder resin Details of the binder resin, the UV initiator, and the silica particles are the same as set forth above.
  • a trace amount of the UV initiator may be present in the coating film. Further, a trace amount of a leveling agent or a dispersion stabilizer may optionally exist in the coating film.
  • the coating film may further include a UV-curable monomer.
  • the UV-curable monomer can include a multifunctional acrylate compound with at least two functional groups, and specific examples thereof are the same as set forth above.
  • the UV-curable monomer may be present in the coating film, as it is chemically bonded with the (meth)acrylate binder resin or the (meth)acrylate compound being introduced in the surface of the silica particle.
  • the coating film may be in the form of a layer built on a certain substrate, or it may be in the form of a processed film capable of being adhered or combined to a product to be applied.
  • a method of producing a coating film includes the steps of mixing a (meth)acrylate binder resin, a UV initiator, an organic solvent, and silica particles having a polylactone-modified hydroxyalkyl (meth)acrylate linked to their surface through a urethane linkage; applying the mixture to a substrate and drying the same; and subjecting the dried mixture to UV curing.
  • the mixing step of the aforementioned components may be uniformly combined by using any method or apparatus commonly available for mixing the organic compounds.
  • the mixture including the (meth)acrylate binder resin, the UV initiator, the organic solvent, and the silica particles may be combined at room temperature by using any typically used mixer or stirrer.
  • the mixture may include 20 % to 80 % by weight of the (meth)acrylate binder resin; 1 % to 10 % by weight of the UV initiator; 5 % to 50 % by weight of the organic solvent; and 1 % to 30 % by weight of the silica particles.
  • the step of applying the mixture one may employ any typical method or apparatus utilized for the application of the coating composition, such as Meyer bar coating, applicator coating, roll coating, and the like.
  • Drying the mixture as applied on the substrate may then be conducted at room temperature for around 24 hours.
  • the drying or curing step may be fulfilled by using an arch-type oven or a floating type oven controlled at a temperature below the boiling point of the solvent as used for the mixture.
  • a PET or TAC (triacetate cellulose) substrate may be employed.
  • the dried mixture may be irradiated with UV rays or visible rays having a wavelength of 200 to 400 nm.
  • the light intensity is preferably from 100 to 4000 mJ/cm 2 .
  • the irradiation time is not particularly limited and may be properly changed depending on the irradiation apparatus, the wavelength of the irradiated rays, or the light intensity.
  • the method of producing the coating film may further include preparing a (meth)acrylate binder resin.
  • the types of the (meth)acrylate binder resin are not particularly limited.
  • Specific examples of the (meth)acrylate binder resin include a urethane (meth)acrylate resin, a hydroxyalkyl (meth)acrylate resin modified with a polylactone compound, a mixture thereof, and a copolymer therebetween. Details of the urethane (meth)acrylate resin and the hydroxyalkyl (meth)acrylate resin modified with a polylactone compound are the same as previously discussed.
  • the step of producing the (meth)acrylate binder resin may include triggering a reaction between an organic isocyanate compound having at least two isocyanate groups per molecule and a polylactone-modified hydroxyalkyl (meth)acrylate resin to produce a urethane (meth)acrylate resin.
  • the organic isocyanate compound having at least two isocyanate groups per molecule and the polylactone-modified hydroxyalkyl (meth)acrylate resin may undergo a urethane reaction, which may be accomplished by stirring the reactants at a temperature of 20 to 100 °C for 1 hour to 10 hours.
  • a metal catalyst such as dibutyltin dilaurate (DBTDL).
  • polylactone-modified hydroxyalkyl (meth)acrylate resin may be a compound of Chemical Formula 1 as described above.
  • organic isocyanate compound having at least two isocyanate groups per molecule may include, but are not particularly limited to, any of a diisocyanate compound as will be described below, a polyisocyanate compound having at least three isocyanate groups prepared by modifying such diisocyanate compound, and the like.
  • modification methods for the diisocyanate compound are isocyanurate modification, trimethylol propane modification, biuret modification, and the like.
  • Any organic compound having at least two isocyanate groups may be used for the diisocyanate compound with no particular limitations.
  • Specific examples thereof include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, hexahydro-1,3-phenylene diisocyanate, hexahydro-1,4-phenylene diisocyanate, perhydro-2,4'-diphen
  • an alkyl acrylate having a hydroxy moiety may be added, and specific examples thereof include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, and the like.
  • the content of the component used in the preparation of the binder resin may be properly controlled depending on reaction conditions and the properties of the binder resin thus obtained.
  • the (meth)acrylate binder resin may be prepared by using 20 % to 60 % by weight of the organic isocyanate compound having at least two isocyanate groups per molecule, 20 % to 60 % by weight of the hydroxyalkyl (meth)acrylate resin modified with the polylactone compound, 10 % to 30 % by weight of a hydroxyalkyl (meth)acrylate, and 0.01 % to 1 % by weight of a catalyst.
  • the mole ratio of isocyanate/hydroxy is preferably between 0.5 and 2.
  • the production method of the coating film may further include a step of preparing silica particles having a polylactone-modified hydroxyalkyl (meth)acrylate linked to their surface through a urethane linkage.
  • the step of preparing silica particles may include subjecting the silica particles to a reaction with a diisocyanate compound, and subjecting a product resulting from the reaction between the silica particles and the diisocyanate compound to a reaction with a (meth)acrylate compound.
  • Any organic compound having two isocyanate groups may be used for the diisocyanate compound without being particularly limited, and specific examples thereof are the same as set forth above regarding the diisocyanate compound.
  • Subjecting silica particles to a reaction with a diisocyanate compound may be conducted by stirring the reactants at a temperature of 20 °C to 80 °C for around 24 hours, and preferably, the reaction occurs in the presence of a metal catalyst.
  • a metal catalyst examples include metals such as platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), palladium (Pd), and tin (Sn), and any organic compounds thereof.
  • the silica particles and the diisocyanate compound may be mixed and react in an organic solvent, and examples of the usable organic solvent are the same as described above.
  • Subjecting the reaction product between the silica particles and the diisocyanate compound to a reaction with the (meth)acrylate compound may be carried out by stirring the reactants at a temperature of 20 °C to 100 °C for 1 hour to 10 hours, preferably in the presence of a metal catalyst.
  • a metal catalyst include metals such as platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), palladium (Pd), and tin (Sn), and any organic compounds thereof.
  • a compound of Chemical Formula 2 can be obtained in the preparation step of the silica particle surface-treated with the (meth)acrylate compound.
  • R 3 is hydrogen or a methyl
  • R 4 is any divalent organic functional group
  • p is an integer of 1 to 5
  • q is an integer of 1 to 10
  • b is an integer of 2 to 9
  • a is an integer equal to or greater than 1
  • "silica" represents a silica particle.
  • R 4 may be a divalent organic functional group derived from the diisocyanate compound, specific examples of which are the same as described above.
  • b can be an integer of 3 to 7, and more preferably 5.
  • a is the number of the hydroxyalkyl (meth)acrylates modified with the polylactone compound, which are linked to surface of the silica particle via the urethane linkage, and for example, ranges from 1 to 30.
  • the production method of the coating film may further include adding a UV-curable monomer to a mixture of a (meth)acrylate binder resin, a UV initiator, an organic solvent, and silica particles.
  • the production method of the coating film may further include adding one or more additives selected from the group consisting of a leveling agent and a dispersion stabilizer to the mixture.
  • UV-curable monomer Details about the UV-curable monomer, the leveling agent, and the dispersion stabilizer are the same as set forth above.
  • a UV-curable coating composition having high transmittance and a low level of haze, excellent scratch resistance, and superb self-healing capabilities, a coating film using the coating composition, and a production method of the coating film are provided.
  • a hexamethylene diisocyanate (HDI) trimer, DN980S (from Aekyung Chemicals, Co., Ltd.) was used for the organic isocyanate prepolymer, and 30 g of Placcel FA-2 and 30 g of Placcel FA-5 (from Daicel Co. Ltd., each being different in the number of caprolactone repeating units per moiety) were used for the polycaprolactone-modified hydroxy acrylate. The reaction was confirmed by an FT-IR spectrum.
  • the coating composition thus obtained was coated onto a PET film 50 times by using a meyer bar and dried in an oven at 60 °C for two minutes, and was then irradiated with UV rays at 100 mJ/cm 2 to produce a coating film.
  • IPDI isophorone diisocyanate
  • a binder resin was prepared in the same manner as set forth in Example 1.
  • a coating composition was prepared in the same manner as set forth in Example 1, except for using 10 wt% of the dispersion of the silica particle surface-treated with acrylate being obtained in section A.
  • IPDI isophorone diisocyanate
  • a binder resin was prepared in the same manner as set forth in Example 1.
  • a coating composition was prepared in the same manner as set forth in Example 1 except for using 10 wt% of the dispersion of the silica particle surface-treated with acrylate being obtained in section A.
  • a coating composition was prepared in the same manner as set forth in Example 1, except for using a silica dispersion of MEK-ST instead of the dispersion of the silica particles surface-treated with (meth)acrylate as obtained from section A of Example 1.
  • the coating composition thus obtained was coated onto a PET film 50 times by using a meyer bar and dried in an oven at 60 °C for two minutes, and was then irradiated with UV rays at 100 mJ/cm 2 to produce a coating film.
  • Table 1 The results of Table 1 indicate that the coating films of the examples show higher transmittance and a lower haze value than the coating film of the comparative example wherein the silica particle dispersion was used as it was, confirming that they have excellent optical properties. In addition, almost no scratches were found even under a load of 200 g for the coating films of the examples, and this evidences excellent scratch resistance thereof. In contrast, the coating film of the comparative example was found to have many scratches created under a load of 200 g.

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  • Chemical & Material Sciences (AREA)
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EP12746954.2A 2011-02-14 2012-02-13 Uv curable coating composition having self-healing capabilities, coating film and method for preparing coating film Active EP2644668B1 (en)

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KR1020120013943A KR101470462B1 (ko) 2011-02-14 2012-02-10 자기 치유 능력이 있는 ｕｖ 경화형 코팅 조성물, 코팅 필름 및 코팅 필름의 제조 방법
PCT/KR2012/001060 WO2012111947A2 (ko) 2011-02-14 2012-02-13 자기 치유 능력이 있는 uv 경화형 코팅 조성물, 코팅 필름 및 코팅 필름의 제조 방법

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EP2644668A2 (en) 2013-10-02
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TW201247811A (en) 2012-12-01
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US8975308B2 (en) 2015-03-10
US20130261209A1 (en) 2013-10-03

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